Conversion of carbonaceous materials into fuels of relatively low boiling point range



Dec. 6, 1932. M. PIER CONVERSION 0F CARBONACEOUS MATERIALS INTO FUELS 0F RELA TIVELY LOW BOILING POINT RANGE Filed NOV. 20, 1928 N wuml i L s \l Patented Dec. 6, 1932 UNITED STATES PATENT? iorljlfcr: A-

. HATHIAS PIER, F HEDELBERG, GERMANY, ASSIGNOR,A BY-MESN ASSIGNMENTS, T0

A .,STANDABD-I. G. COMPANY, 0F LINDEN, NEW JERSEY, A CORPORATIGN 01'1A DELA- convnnsroN-or 'oAnBoNAcnoUs MATERIALS INT0 FUELS or nnLa'rIvELY Low BoILING POINT' RANGE' f l Application led November 20, 1928, Serial No. 320,765, and in Germany December 17, 1927.

Thepresent invention relates to the conversion of carbonaceous materials into fuels of comparatively low boiling point range.

The conversion of various kinds ofj'coal into hydrocarbons by irst treating them with hydrogen at .elevated temperatures and .high

pressures, and then subjecting the products so obtained tothe same treatmentbut in the presence of catalytic substances, hasa'lready been described. It has further been suggested, that especially vthe middle oils can l' to be treated should be free from high molec- .li uefaction of coal.

be advantageously converted into benzine by the employment of catalytic substances because by the use of the said oils the activity of the latter is maintained for a long time. -It is important, however, that the middle oils ular carbon compounds since these may choke the catalysts and render them inactive. Such compounds are generally still present in the crude products obtained have now found that carbonaceous mate- 'rials such as substances of the nature of coal, tars, mineral oils and the .like are converted .into-liquid Afuels of relatively low boiling point range such as benzine, middleroils and illuminating oils by destructive hydrogena- .tion (which process, as is known, is effected at temperatures between 300 and .7009 C. and under elevated pressures of more than atmospheres, in the presence of hydrogen or gases containing or supplying the same. for example water vapor, easily decomposable hydrocarbons' or hydrogen chlorid, andv preferably'in the presence ofV catalytic sub- 'tances) in more than one stage, by removing to a considerable extent the carbonaceous substances of high molecular weight, contained in the vaporous products, which disturbthe` further refining from thesvaporous-products 'obtained in the irst stage, or if desired alsoin l later stages, before subjecting the latter to a treatment in a further stage, but without condensing appreciable quantities of other substances s'uitable for further refining. As examples of such carbonaceous substances of high molecular weight disturbing refining maybe mentioned vfor examplel heavy oils of high -boiling point range, asphaltic and directly from the pitchy substances, phenols of high boiling point and the like. The injurious substances should at the most-be present in only such small quantities that any harmful iniluence on the catalytic substance employed in .the second or later stages is avoided.v The per missible concentration of these harmful sbv stances depends in particular on the porosity of vthe catalysts employed in the secondv and later stages.

The process may be carried out for\ example by removing the injurious substances from the vapors by passing them over solid masses, for example absorptive masses such as-active carbon, active silica and the like, by which the injurious substances areretained.l Ak fractionating device may also be attached behind the rst reaction chamber, 5

and herein the high molecular'v carbonaceous substances, such for example as heavy oils,

are removed, so that theydo not come into contact with the catalysts Aemployed ina later stage, while the fractions to be further treat ed pass through uncondensed. Liquid 'Aabsorpti'on agents may also be employed. 3

The process may also be carriedfout by making the linear velocity of the current of the substance to be converted in the irst f'kt'is preferable to operate in such a manner that the products to--be treated are treated u in the first stage in theliquid'phase at such a temperature that the injurious products,-

which for example would cause injury to the..

catalysts in a later stage, are not`evaporated. a

In the different stages of the processlin accordance with the present invention,suit able catalytic substances are employed, for

example, when operating inthe liquid phase, ,Y

it is advantageous to employ them ina'form very finely distributed in the liquid. In this case it mayin some cases advantageous in order to attain a high ellect to treat .the catalysts or the liquidscontaining the same in high-speed mills, for example in colloid mills. It is advisable to take care'that substances Which give rise to injurious reactions, such as deposition of carbon, formation of methane andthe like,-are excluded from the parts of the apparatus which come into contact with the hot reacting materials.

The initial materials in accordance with the present invention may be wholly or partially worked up into benzines. At Iappropriate places inthe apparatus oils may be drawn off, Whic may-be used for example as scrubbing oils for-pasting up coaly initial materials, or as initial material in the manufacture of lubricating oils. I

Catalysts particularly suitable for the process of the present invention, both for the processof destructive hydrogenation proper and for the conversion of the noxious substances of high molecular Weight. are those immune against poisoning by sulfur or its compounds.' As examples of such lcatalysts may be mentioned catalysts comprising,

compounds containing sulfur in coinbnation, for example metallic sullids, in particular the heavy metal sulfids and more especially those of the. iron group, either alone or as mixtures with one another or p with metals, metalloids. active charcoal, coke s'ulfid, nickel sulfid, manganese sulid andC .cf cobalt sullid or the like or with oxids, hydroxids, or carbonates, or with other materials of a`catalytic or of inert nature. "The sulfur may also be combined with the catalyst by adding sulfites or sulfates thereto or by the addtionof sulfur to metals or oxids. A very suitable cata'- lyst may' be obtained by treating iren with hydrogenv suld at an elevated temperature. Particularly'suitable catalysts of this class are for example cobalt sulfid, iron sulid, zinc the like or mixtures thereof, for example, mixtures' of cobalt su'lfid with nickel sulfid or l with manganese sulfid, or ofcobalt sulfid mixed with iron sulid ,or with zinc sulfidor with aluminium sulfid, with or without an addition of inert slibstances'. Catalystsfcon'ssting of or containing molybdenum, chromium. uranium or tungsten or the compounds thereof or mixtures of thosesubstances are also particularly suitable. As examples of this. type of catalyst may be mentioned molybdic acid or ammonium molvbdate. tungsten sulfid, tunastic acid, uranium oxid,A chromium hydroxid and chromic acid. Mixtures ofl chromium or tungsten with other-catalysts such as with cobalt, nickel or iron may also be employed. Activatin of the catalysts or the addition of substances tage, .this being effective -for example 'with one of the elements silver, copper,

increasing their mechanicalstrength may also be of 'advan- :amples may be ymentioned or calcium carbonate. of aluminium silicate with advantage.A

Carriers such as lumps may also be employed As further catalysts may `be ,mentioned oxidic, catalysts comprising `zin'c oxid, chromium oxid or manganese oxidv as are comparatively stable against the action of water, for example silicon nitri'd or titanium nitrid. These said oxidic. catalysts maybe employed in conjunction with other substances such as lumps of lire-clay, quartz, asbestos, pumice, coke, als, in particular heavy metals. metalloi'ds, oxids, sulfids, C'farbids, andthe like and mixtures thereof with the said substances. As still further examples of suitable catalysts may be mentioned such containing atleast cadmium, lead, bismuth, tin in the form of its compounds, further the diliciiltly .red'ucible such as magnesia,

metal oxids or carbonatos, lithium carbonate, boric acid, alumina, the rare earths, including the diflicultly reducible oxids of metals frointhe 4th group ofthe periodic,- system, ganese or vanadium. The catalysts may contain several of these substances or also other substances, for example metalsfrom the 8th .group of the `periodic system, such as iron.

As specific examples of these catalysts may be mentioned such obtained by impregnating' porous refractory materials with solution of lead nitrate, or of stannous chlorid, silver nitrate or of copper hydroxi'd, either alone or in admixture with'compounds of iron, co-

latter compounds may active charcoal, metor the oxid's of zinc, manv balt and the-like. Further may be mentioned alvsts containing active charcoalor the metn alloids boron, silicon, phosphorus', arsenic,

selenium, tellurium o r the compounds thereof orhalogeiis. These metalloidsma'y advantageously be employed together with elements from the 2nd to the '8th group of the periodic system, from' the' 6th group 'of the periodic system.

in particular .such selected.

'The catalysts may -for example contain thefollowing acids or their saltsnamely phosphoric acid, arsenious acid, silicicacid, boric' acid, hydrofluoric acid. .hydrochloric acid, l

seleniousacid .and the like. As specific e alder-wood charcoal'pwhich has been glowed silicon carbid,

at 800 C. and'impregnated with phosphoric acid, calcium lyphosphate, molybdenum phosphate, tungsten phosphate, iron phosphate, aluminium phosphate, arsenious acid together with molybdenum 'or tungsten, silicids, for example iron silicid containing 15 per cent of silicon, active silica, hydrosilicates, borids such as titanium borid or iron borid, calcium iuorid, molybdenum with 10 per lcent of aluminium chlorid, molybdenum with 10 per cent of cadmium .chlorid,molybdic acid with sodium selenite. Compounds containing xed nitrogen may also be employed with advantage inthe' reaction. `Thus ammonia or its salts, for example, ammonium sulfid and in some cases organiccompounds of nitrogen may also be advantageous.' Such nitrids as are fairly stable against the action of watr have been found to give particularly good results. As further examples of suit! able catalysts may be mentioned, such containing one or more elements fromthev a (4th to the 8th group of the periodic system, in particular Asuch from the v6th group' of the periodic system and more particularly molybdenum) together with I) (small amounts of other elements-from the 2nd to the 7th group of the periodic system or cop- 'per or gold or the comnoundsthereof) The elements from the 2nd and 3rd group may, however, also be employed in large amounts.

'Thus mixtures containing molecular proportions of molybdic acid -with magnesia or with copperor with aluminium hydroxid, or mixtures of tungstic acid with zinc oxid or of vanadium oxid with magnesia furnish good results. Excellent catalysts are further molybdic acid with'about 10 per cent of chromium oxid or of` vanadium oxid, molybdic acid with about 10 per cent of uranium oxid or of thorium oxid or Aof manganou's oxid, further tungstic acid Vcontaining about 10 per cent of chromium oxid or of a mixture of uranium oxid, cobalt and a small amount of chromium oxid. Again another very suitable class of catalysts is formed by the noble metals vor lead or tin or compounds thereof on carriers, in particular on magnesia or magnesite or chromiuln oxid. As examples of this. class of catalystv may be mentioned ruthenium, palladium, platinum, gold, lead or tin or magnesia or jma esite or platinum `or gold or chromium oxid.l Catalysts containing small amounts of silver or of mixtures of copper with aine or with cadmium Ain a free state or in chemical' combination and preferably also boron or aluminium or l siliconl or titanium, or vanadium, or tantalm orl chromium or molybdenum or tungsten or cobalt in a free or combined state or mixtures of these are also very suitable. Examples ofl such catalystsl are tantalic acid containing v10 per cent of silver, molybdic acid containing 10 per cent of silver or silica containing 10 percent of a mixture of copper and zinc. Again another class of catalysts'consists of refractory metals or alloys on which small amounts of solid oxids of elements having a catalytic action from the 3rd to the 7th group of the periodic system have been deposited. The said metals'or y their alloys are preferably employed in an etched condition and preferably aciditied solutions of salts of the said oxids are employed as the etching agent. Such catalysts as are employed in the production of methanol from hydrogen and oxids of carbon are also very suitable. I v 4 c The process pretcrabiy carried out at elevated pressure such as about 2,0, 50, or

1 50 atmospheres, although when a very thorough react1on is desired, higher pressures such as 200, r500, 1000 or even more atmos-Y pheres-may'be employed. On the other. hand it may in some cases be of advantage to carry out the process under atmosphericpressure.

'The temperatures employed should. always be above'the decomposition point' of the initial material, and usually range between about 300 and 700 C.

The accompanying drawing shows in la diagrammatic manner an apparatus, 4'partly in section, .in which the process according to the present invention may be carried-out.

A hydrocarbon oil to be converted is sup*- pliedat s and pumped by means o pump 'v into the heating coil q. Hydrogen is simultaneously supplied at t and pumped by means of pump u into the same heating coil g. "The Ahot mixture of hydrocarbon oil and hydrogen is supplied 'at a into the first hydrogenating vessel b which is filled with a catalyst prepared from molybdic acid, chromic acijd and manganese carbonate and-which is keptat a temperature of about 420 C. 'The vaporous mixture formed is led together with the excess of hydrogen without' releasing the pressure through the pipe c into a condensing apparatus Z filled with an adsorptvc mass, such as active carbon and provided with a cooling coil fw through which water is passed. In this condensing apparatus d the parts boiling above 350 C. are substantially condensed and are returned to tbe reaction .vessel b. The gases andvapors not condensed pass through pipe e into a heating coil. m and from thence into a second hydrogenating vessel f which is filled with acatalyst'prepared' from molybdic acid, zinc oxide and manganese oxlde and which is kept ata temperature of about 47 0 C. Fromthe reaction vessel f the vaporous mixture formed passes bv way i of the pipe g topa condenser The condenser liquids are gathered in the vessel z' and drawn off at o. The uncondensed parts are drawn off at Z. 60 per centof the liquid'products boil up to 200 C.` the rest up to 325 C; Residues formed in the hydrogenating vessel I) are drawn 'off at p. By this manner of work-4 ing the.` activity of .the catalyst in preserved fora long time whereas-the catalyst is soon rendered inactive when kthe parts boiling above 350 issuing from b are not'removed at da The following examples will further illus-v l trate the nature of the invention but -the invention is not restricted thereto. The parts are by weight.

' i x- Example mospheres -pressure. Thev reaction product 4 btained is passed in the form of vapor first over a catalytic'substance comprising molybdenum and zinc atthe same temperature and then at 460.C. over a. catalytic substance v consisting of trio'xids of molybdenum and chromium. A product containing 80 to 90 .per cent vof benzine,l free from phenol anda consisting mainly of saturated hydrocarbons is thus obtained in a continuous operation; l By the employment lofthe prearranged catalytic substance comprising molybdenum 'and zinc `theinitial high yield is maintained during' the 'continuous operation. Instead of the said catalyti'dsubstance, active carbon or other absorptive agents'may be employed which are renewed either continuously or from time to time. v

Example 2 parts of tinely`ground pit coal made up into, a paste with 50 parts of an oil residue, obtained in a destructive hydrogenation process, are treated at 450 C. and under a pressure of 200 atmospheres with hydrogen in the Ipresence of a catalyst containing i' v'molybdenum and zinc.- vPart of the said oil residue is converted into benzine and middle oil and issues as such from the apparatus. The2 residual partof higherboiling point is separated from the solid residues and is treatvedinthe liquid phase atl a temperature of 400 to 440 (hand under a pressure of,200 atmospheres with hydrogen in thenpresence of a catalyst containing molybdenum, mangapese and chromium. The vaporous products.

luing from the reaction vessel .are freed from. oils of high boilingpoint range, which rwould have an undesirable influencein the further stages of the process, by being passed over active charcoal and are'then treated with hydrogenat 460 C. and 4under a presf sure of 200 atmospheres in the presenceof a catalyst containing molybdenum,v chromium and aluminium.

A good yield of a produc of the nature of benzine isobt'ained which as no tendency to knocking when employed as a fuel `for internal-combustion engines andwhich may also be' employed with advantage as an addition C. of the vaporous products` E'aanple 3 Brown coal producer tar is passed together with hydrogen at 420 C. and under a pressure of 200 atmospheres over a catalyst produced from molybdic oxid, chromic oxid and manganous carbonate; The yaporousV mixture Vthus obtained is passed without releasing the pressure in to a condensing vessel, the

temperature of which is so adjusted' that those constituents which under normal pressure'boil above about 350 C. are 'separated olii'. These may bd run -oi from the reaction vessel and amount to' about 1 0 per cent by p'erature of 470 C. over a catalyst consisting .weight of the vaporous products present inall. The residual vapors are passed at a temof molybdic oxid, zinc oxid and magnesium oxid. In this manner a product is obtained, 60 per cent of which distil at temperatures` below 200 C., whereas the remainder passes over-at temperatures up to about 325 C.

- The activity of the second catalyst is maintained uniformly excellent for 'alongtime accordingto this manner ofworking, whereas, without a preliminary separation of the` constituents. boiling above 350 C., the activity ofthe catalyst soon decreases on ac.-

count of condensations on the surface thereof. The rate of flow of the vaporous mixture which -in the first reaction vessel is usually adjusted at about 1.5' to 2 centimeters per second, is preferably lowered n the stripper, for example by suitably widening=the crosssectional area of this part; in the second rc? action vessel the rate of ilow of the gases may be increased to about'4 to per second. WhatI claim is 1. In the conversion of carbonaceous materials into liquid fuels of relatively low boiling point range by destructive hydrogenation at a temperature between 300 and 700 C. and under a pressure of more than 20 atmospheres in more than one stage in the presence of catalytic substances, the step of removing suhstantally all the carbonaceous substances of high molecular weight, which dist-urb the further conversion` contained inpthe vaporous products derived from the first stage of the process, without appreciably depreciating the quantity of substancesspitable for furher conversion prior to afurther destruc- 5A centimeters .tive hydrogenation of sa" d vaporous products with a catalyst subject to cloggingby said substances of high molecular weight.

2. In the conversion of carbonaceous materals into liquid fuels of relatively low boiling point range by destructive hydrogenation at as temperature between 300 andy P version, contained in the Vaporous products,

state, and in the presence of catalytic substances the step Vof removing substantially all the carbonaceous substances-of high molecular weight, which disturb the further conversion, contained in the vaporous products obtained in the first stage of the process, without appreciably depreciating the quantity of substances suitable for further conversion prior to a -further destruct/ive hydrogenation ,of said vaporous products with a catalyst sub1 :ject to cloggin by said substances of high molecular weig t.'

3.` In the conversion of carbonaceous materials into liquid fuels' of relatively low boiling point range by destructive hydrogenation at a temperature between 300 and ,700 C. and under a pressure of more than '20 atmospheres in more than one stage in the depreciating the quantity of substances suitapresence of catalytic substances the step of removing substantially all -the carbonaceous substances of high molecular weight, which disturb the further conversion, contained in the vaporousproducts obtained pror to' the last stage of the process without appreciably ble for further conversion prior to a further destructive hydrogenation of said vaporous products in the last stave of the process with a catalyst subject to c ogging by said sub- -stances of high molecular weight.

4. In the converson of carbonaceous materials into liquid fuels of relatively low boiling point range by destructive'hydrogena- 351V t1on at a temperature between 300 and.v

700 C. and under a pressure of more than 20 atmospheres in more than one stageat least the first stage being carried out in the liquid state, and in the presence 'of catalytic substances, the step of removFng substantially all the carbon'aceous substances of high molecular weight, which disturb the further conversion, contained in the vaporous products lobtained prior to the last stage of the process, without appreciably depreciating the quantities of substances suitable @for further conversion prior to a further destructive hydroderived from thefrst stage ofthe process, without 'a precably de reciating the quantity of su stances suita le for further conversion prior to a further destructivehydrogenation of said vaporous products with a catalyst subject to clogging by -said substances of high molecular weight;

6. In the conversion of carbonaceous materials into liquid fuels of relatively low boiling point range by destructive hydrogenation at a temperature between 300 and 700 C. and under a pressure of more than 20 atmospheres in more than one stage, the first stage ing carried out in the liquid state, and in the presence of a catalyst immune from.

poisoning by sulfur, the step of removingV substantially all-the carbonaceous substances of high molecular weight which disturb the further conversion, contained inthe vaporous products, issuing from the first stage of the process, Without appreciably depreciating the-quantity of substances suitable for further conversion prior toa further de.

structive hydrogenation of saidl vaporous products with a catalyst subject to'clogging by said substances of high molecular weight.

7. In the conversion ofcarbonaceou's ma` t'erials into liquid fuelsof relatively low boiling point range by destructive hydrogenation ,at a temperature-between 300 and 700 C.

and under a pressure of more than 20 atmos' pheres 4in more than one stage, and in the v presence of a `catalyst immune from poisoning by -sulfur, the step of removing substantially all the carbonaceous substances of high molecular weight, which disturb the further conversion, contained in the vaporous products obtained prior, to the laststage'of the process, without appreciably depreciatingthe quantities of substances suitable' for further conversion prior to a further destructive..hydrogenation of said vaporous prod ucts in the last stage of the process with ,a catalyst subject to clogging by said substances of high molecular weight. v

8. In lthe conversion of carbonaceous ma'- terials into liquid fuels of relatively low boiling pointrange by destructive hydrogenation at a temperature between 300 and 700 C.v

and under a pressure of more than 20 atmos` pheres in more than one stage, at least the first stagebeing carried out in the liquid state, and in the presence of a'catalystvimvmune fromoisoning by sulfur, the step :of

removing su stantially all the carbonaceous substances of high molecular weight., Vwhich disturb the further conversion, contained in the vaporous products obtained priorto the laststage of the process, without'appreciably depreciating the quantity of substances suita ble for further conversion prior to a further destructive hydrogenation of said vaporous products with a catal st subject to clogging by said substances ofy igh molecular weight.

, 9. In the conversion of carbonaceous materials into liquid fuels of relatively low boiling point range by destructive hydrogenation Aat a temperature between'300 and 700 C. e and under a pressure of 'more than 20 atmospheres inmore than one stage in the presence i V r of catalytic substances, the step of removing the carbonaceous substances of high molecfrom the first ular weight, which disturb the further conversion, from the .vaporous products issuing stage ofthe process by means of an adsorbent, without condensing appreciable quantities of substances suitable -for further'conversion prior t0 a further destructive hydrogenation.' l 10. In the rconversion of carbonaceous materials into liquid fuels of relatively low boillat a temperature between 300 and under a pressure of more than 20 atmos-` ing pont range by destructive hydrogenation 'and 700 C..

heres in more than one stage, at least the hrst stage being` carried outin the liquid state, and in the presence of catalytic Vsubstances, the step of removing the carbonaceous substances of high molecular weight, which disturb tlie' further conversion, from the vaporous 'products issuing` from the firststage of the process by means of an adsorbent,

without condensing apprecable quantities of substances suitable for .further conversion prior to a further' destructive hydrogenation.` v11`- In the converslon of carbonaceous-materials into liquid fuels of relatively low boiling point range by destructive hydrogenation at a temperature .between 300'and 700 C;

and under a'prcssure of more' than 20 atmospheres in more than one stage in the presence of cata-lytic substances, the step of removing the carbonaceous substances 'of high molecular Weight, which .disturb the further conversion, from the vaporous products obtained prior to the last stage of the ,process by means of an adsorbent, lWithout; condensing aping up the said initial material preciable quantities of substances suitable for further conversion prior'to a further destructivehydrogenaton in th last stage of the process. V

"12;. A In the conversion of carbonaceous materials into liquid fuels of relatively low boiling point range by destructive hydrogenation at a temperature between' 800 and l700 C. and under a pressure of more than atmospheres in more than one stage, atleast the first stage being carried out in the liquid state, and

1n the' presence of -catalytc substances, the step of removing the carbonaceous substances of high molecular weight, which disturb the l further conversion, from the Vaporous products obtained prior to the last stage of the processby means of an adsorbent, Without condensing appreciable quantities of substances suitable for further conversion prior to a further destructive hydrogenation in the last stage of the process.. y

13. The process for the conversion of pit coal'into4 liquid fuels of comparatively low boiling point by destructive hydrogenation in more than one stage which comprises makwith oil, treating it at about 450 C. and under a pressure of about 200 atmospheres .my hand.

into .a paste with hydrogen in the presence of a catalyst containing molybdenum and zinc, freeing the vaporous products issuing froem the reaction .vessel from theicarbonaceous substances of MATHIAS PIER. a

ioo 

